Laminate comprising curable epoxy film layer comprising a di-isoimide and process for preparing same

ABSTRACT

The present invention deals with a laminate useful for forming fully encapsulated flexible printed wiring boards. The laminate comprises a dielectric substrate coated with a curable composition comprising an epoxy and a novel aromatic di-isoimide chemical compound. The curable composition provides the benefit of thermal latency, improving shelf-life, and reducing premature curing during processing. Fully encapsulated printed wiring boards are also disclosed.

RELATED PATENT APPLICATIONS

This patent application is related to U.S. patent application Ser. No.13/168,047, entitled “Curable composition comprising a di-isoimide,method of curing, and the cured composition so formed;” U.S. patentapplication Ser. No. 13/168,024, entitled “Di-isoimide Composition;”U.S. patent application Ser. No. 13/168,069, entitled “Printed wiringboard encapsulated by adhesive laminate comprising a di-isoimide, andprocess for preparing same;” and, U.S. patent application Ser. No.13/168,081, entitled “Process for Preparing a Di-Isoimide Composition.”

FIELD OF THE INVENTION

The present invention deals with a laminate useful for forming fullyencapsulated flexible printed wiring boards. The laminate comprises adielectric substrate coated with a curable composition comprising anepoxy and a novel aromatic di-isoimide chemical compound.

BACKGROUND OF THE INVENTION

Epoxy compositions are widely used in many applications including, amongothers, the electronics industry. In some applications they are blendedwith rubber to provide enhanced flexibility, toughness, and adhesivestrength. One such application is as a flexible cover layer for flexibleprinted wiring boards.

While epoxies offer many desirable properties, they are known to beundesirably flammable, often requiring the addition of a flame retardantto a curable epoxy formulation in order to meet fire resistancestandards. In addition, it is desirable to have a curable epoxycomposition with as long a shelf life as possible. One approach toachieving long shelf-life is to prepare a so-called latent curingcatalyst or cross-linking agent (curing agent). A latent catalyst orcuring agent could be inactive at room temperature but thermallyactivated at a temperature well above room temperature. For practicalreasons, it is desirable for uncured compositions to remain stable attemperatures up to 40 or 50° C. Thus a latent catalyst or curing agentactivated at a temperature above 50° C. but below a temperature thatwill degrade the epoxy or electronic circuit elements is highlydesirable in the art. A catalyst or curing agent that further obviatesthe need for a flame retardant additive would be so much the better forthe properties of the resultant composition.

SUMMARY OF THE INVENTION

The composition of the present invention provides a curing catalyst andcross-linking agent suitable for use in a curable epoxy composition, acurable epoxy composition prepared therewith, a cured compositionprepared therefrom, a film or sheet coated with the curable composition,and an encapsulated printed wiring board comprising the curedcomposition.

In one aspect, the present invention provides a di-isoimide compositionrepresented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.

In another aspect, the invention provides a first process for preparinga di-isoimide composition represented by the Structure I, the processcomprising mixing, at a temperature in the range of −10 to 160° C., in afirst solvent pyromellitic dianhydride (PMDA) with a substituted orunsubstituted di-amino triazine represented by the Structure II

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.

In a further aspect, the present invention provides a curablecomposition comprising a solvent having mixed therewithin an epoxy and adi-isoimide composition represented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.

In a further aspect, the present invention provides a second processcomprising heating the curable composition hereof to a temperature inthe range of 100 to 250° C. for a period of time in the range of 30seconds to 5 hours, thereby forming the corresponding cured composition.

In another aspect, the present invention is directed to a laminatedarticle comprising a substrate and a coating deposited thereupon whereinsaid substrate is a polymeric sheet or film and said coating comprises acurable composition comprising a second solvent having mixed therewithinan epoxy and a di-isoimide composition represented by Structure I.

In a further aspect, the present invention is directed to a printedwiring board comprising in order a first layer of a first dielectricsubstrate, a second layer of one or more discrete electricallyconductive pathways disposed upon said first dielectric substrate, athird layer of an adhesively bonding layer in adhesive contact with saiddiscrete electrically conductive pathways, and a fourth layer of asecond, flexible, dielectric substrate, said adhesively bonding layercomprising a curable composition comprising a second solvent havingmixed therewithin an epoxy and a di-isoimide composition represented byStructure I.

In another aspect, the present invention provides a process forpreparing an encapsulated printed wiring board, the process comprisingadhesively contacting the coated surface of a laminated article having asurface with a coating disposed thereupon to at least a portion of thediscrete conductive pathways disposed upon a dielectric substratethereby forming a multilayer article; and, applying pressure to theprinted wiring board so formed at a temperature in the range of 100 to250° C. for a period of time in the range of 30 seconds to 5 hours,thereby forming an encapsulated printed wiring board; wherein saidprinted wiring board comprises in order a first layer of a firstdielectric substrate, a second layer of one or more discreteelectrically conductive pathways disposed upon said first dielectricsubstrate, a third layer of an adhesively bonding layer in adhesivecontact with said discrete electrically conducting pathways, and afourth layer of a second, flexible, dielectric substrate, saidadhesively bonding layer comprising a curable composition comprising asecond solvent having mixed therewithin an epoxy and a di-isoimidecomposition represented by Structure I.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic representation of the process hereof for creatingthe printed wiring board hereof, as described in Example 12.

DETAILED DESCRIPTION OF THE INVENTION

The term “epoxy” refers to a polymeric, generally an oligomeric,chemical comprising epoxide groups. A cross-linking agent suitable foruse in the processes disclosed herein is a multifunctional moleculereactive with epoxide groups. The cross-linked reaction product thereofis the reaction product formed when the cross-linking agent reacts withthe epoxide or other group in the epoxy molecule. The term “epoxy” isconventionally used to refer to the uncured resin that contains epoxidegroups. With such usage, once cured, the epoxy resin is no longeractually an epoxy. However, reference to epoxy herein in the context ofthe cured material shall be understood to refer to the cured material.The term “cured epoxy” shall be understood to mean the reaction productof an epoxy as defined herein and a curing agent as defined herein.

The term “cured” refers to an epoxy composition that has undergonesubstantial cross-linking, the word “substantial” indicating an amountof cross-linking of 75% to 100% of the available cure sites in theepoxy. Preferably more than 90% of the available cure sites arecross-linked in a “fully cured” epoxy composition. The term “uncured”refers to an epoxy composition when it has undergone littlecross-linking. The terms “cured” and “uncured” shall be understood to befunctional terms. An uncured epoxy composition is characterized bysolubility in organic solvents and the ability to undergo plastic flowunder ambient conditions. A cured epoxy composition suitable for thepractice of the invention is characterized by insolubility in organicsolvents and the absence of plastic flow under ambient conditions. It iswell-known in the art that some of the available cure sites in anuncured epoxy composition could be cross-linked and some of theavailable cure sites in a cured epoxy composition could remainuncross-linked. In neither case, however, are the distinguishingproperties of the respective compositions significantly affected.

The art also distinguishes a partially cured epoxy composition known asa “B-stage” material. The B-stage material may contain up to 10% byweight of solvent, and exhibits properties intermediate between thesubstantially cured and the uncured state.

For the purposes of the present invention the term “curable composition”shall refer to a composition that comprises all the elements necessaryfor producing a “cured” composition, but that has not yet undergone the“curing process” and is therefore not yet cured. The curable compositionis readily deformable and processible, the cured composition is not. Theterms “curable” and “cured” are similar in meaning, respectively, to theterms “crosslinkable” and “crosslinked.”

While the invention is not limited thereto, it is believed that the curereaction of an epoxy with the di-isoimide hereof is mostly a reaction ofan amine group of the di-isoimide to open the oxirane ring (or epoxygroup, as it is often referred to) resulting in a nitrogen carbon bond,and an alkyl hydroxyl group. So in the above instance, the di-isoimideserves as a cross-linking agent. When, for example, a phenolic novolacis also present, the oxirane ring opening reaction is effected primarilyby the reaction of the phenol hydroxyl group of the novolac with theoxirane ring, thereby creating an oxygen-carbon bond and an alkylhydroxyl group. When a more active cross-linking agent, such as thephenol is not present, the di-isoimide serves as both cross-linkingagent and a catalyst.

The terms “film” and “sheet” refer to planar shaped articles having alarge length and width relative to thickness. Films and sheets differonly in thickness. Sheets are typically defined in the art ascharacterized by a thickness of 250 micrometers or greater, while filmsare defined in the art as characterized by a thickness less than 250micrometers. As used herein, the term “film” encompasses coatingsdisposed upon a surface.

The term “discrete conductive pathway” as used herein refers to anelectrically conductive pathway disposed upon a dielectric substrate inthe form of a film or sheet which leads from one point to another on theplane thereof, or through the plane from one side to the other.

There are several terms that are repeated throughout this invention thatare described in detail only upon the first mention thereof. However, inorder to avoid prolixity the descriptions of the term are not repeatedwhen the term reappears further on in the text. It shall be understoodfor the purposes of the present invention that when a term is repeatedin the text hereof, the description and meaning of that term isunchanged from and the same as that provided for the term upon its firstmention. For example the term “di-isoimide composition represented byStructure I” shall be understood each time it appears to encompass allthe possible embodiments recited with respect to Structure I upon itsfirst appearance in the text. For another example, the term “secondsolvent” shall be understood to refer to the same set of solventsdescribed for the “second solvent” at the first appearance of the termin the text.

For the purposes of this invention, the term “room temperature” isemployed to refer to ambient laboratory conditions. As a term of art,“room temperature” is normally taken to mean about 23° C., encompassingtemperatures ranging from about 20° C. to about 30° C.

The term “printed wiring board” (PWB) shall refer to a dielectricsubstrate layer having disposed thereupon a plurality of discreteconductive pathways. The substrate is a sheet or film. In one embodimentof the invention the dielectric substrate is a polyimide film. In afurther embodiment, the polyimide film has a thickness of 5-75micrometers. In one embodiment the discrete conductive pathways arecopper.

PWBs suitable for the practice of the present invention can be preparedby well-known and wide-spread practices in the art. Briefly, a suitablePWB can be prepared by a process comprising laminating a copper foil toa dielectric film or sheet using a combination of an adhesive layer,often an epoxy, and the application of heat and pressure. To obtain highresolution circuit lines (≦125 micrometers in width) photoresists areapplied to the copper surface. A photoresist is a light-sensitiveorganic material that when subject to imagewise exposure an engravedpattern results when the photoresist is developed and the surfaceetched. In a suitable PWB, the image is in the form of a plurality ofdiscreet conductive pathways upon the surface of the dielectric film orsheet.

A photoresist can either be applied as a liquid and dried, or laminatedin the form, for example, of polymeric film deposited on a polyesterrelease film. When liquid coating is employed, care must be employed toensure a uniform thickness. When exposed to light, typically ultravioletradiation, a photoresist undergoes photopolymerization, thereby alteringthe solubility thereof in a “developer” chemical. Negative photoresiststypically consist of a mixture of acrylate monomers, a polymeric binder,and a photoinitiator. Upon imagewise UV exposure through a patterningphotomask, the exposed portion of the photoresist polymerizes andbecomes insoluble to the developer. Unexposed areas remain soluble andare washed away, leaving the areas of copper representing the conductivepathways protected by the polymerized photoresist during a subsequentetching step that removes the unprotected conductive pathways.

After etching, the polymerized photoresist is removed by any convenienttechnique including dissolution in an appropriate solvent, or surfaceablation. Positive photoresists function in the opposite way withUV-exposed areas becoming soluble in the developing solvent. Bothpositive and negative photoresists are in widespread commercial use. Onewell-known positive photoresist is the so-called DNQ/novolac photoresistcomposition.

Any PWB prepared according to the methods of the art is suitable for usein the present invention.

In one aspect, the present invention provides a di-isoimide compositionrepresented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted. In one embodiment, R₁ is NH₂.

In another aspect, the present invention provides a first process thatcan be used to prepare the composition represented by the Structure I,the first process comprising mixing in a first solvent, at a temperaturein the range of −10 to +160° C., PMDA with a di-amino triazinerepresented by the Structure II

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.

In one embodiment, R₁ is NH₂.

Suitable first solvents include but are not limited to polar/aproticsolvents characterized by a dipole moment in the range of 1.5 to 3.5 D.While the reaction between the aminoazine and PMDA takes place insolution, full miscibility of the reactants in the solvent is notnecessary. Even limited solubility will permit the reaction to proceed,with additional reactants dissolving as they are consumed in thereaction. Suitable solvents include but are not limited to acetone,methyl ethyl ketone (MEK), methyl isobutyl ketone, ethyl propionate,ethyl-3-ethoxy propionate, cyclohexanone, and mixtures thereof. Mixturesthereof with small amounts (for example, less than 30% by weight) ofnon-polar solvents such as benzene are also suitable. In one embodiment,the solvent is cyclohexanone.

When the dipole moment is below 1.5 D, solubility of melamine, alreadylow, becomes so low that the reaction can take weeks to go tocompletion. When the dipole moment of the solvent exceeds 3.5 D the rateof the reaction converting the di-isoimide to di-imide can proceed at aninconveniently rapid rate, causing excessive loss of the desireddi-isoimide.

According to the first process of the invention, PMDA and a suitablediamino triazine, substituted or unsubstituted, as described supra, arecombined in the presence of a suitable first solvent, and allowed toreact. The reaction temperature can be in the range of −10 to +160° C.The yield of di-imide increases with increasing temperature, at theexpense of the di-isoimide. While this invention is directed to thepreparation of and the advantageous use of the di-isoimide, the presenceof some di-imide mixed in with the di-isoimide does not necessarily haveany particularly negative impact. In some instances, it could beadvantageous to use a higher reaction temperature which results in lowerselectivity but higher reaction rate.

In general, higher reaction temperature corresponds to faster reaction.Selectivity depends on temperature and the specific choices ofdianhydride, triazine, and solvent. For example PMDA and melamine incyclohexanone produce pure isoimide at 25° C., almost pure isoimide at50° C., and produce about 80% isoimide at reflux (˜155° C.). PMDA andmelamine react faster in N,N-dimethyl formamide (DMF) than incyclohexanone at the same temperature but the reaction continues on toform imide from a di-isoimide intermediate if the reaction is notstopped in time.

In one embodiment, the reaction temperature is in the range of roomtemperature to 100° C. In a further embodiment, the reaction temperatureis in the range of room temperature to 50° C.

The first process hereof does not require a water scavenger (such astrifluoroacetic acid) in order to provide the desired di-isoimide asrepresented by Structure I. It is highly preferred in the first processhereof to omit any water scavenger, in order to avoid havingsubsequently to remove the water scavenger after reaction is complete.

It is observed in the practice of the invention that the di-isoimidehereof is more soluble than the analogous imide in relatively mild, lowboiling point solvents such as cyclohexanone and MEK. Much stronger highboiling point solvents, such as dimethyl acetamide (DMAC) orn-methylpyrrolidone (NMP), are required to dissolve the imide. Thisfeature of the di-isoimide hereof is of considerable importance in theformulation of epoxies with practical commercial applicability. It isdifficult to remove high boiling point solvents without also initiatingthe epoxy cure. For adhesive applications, particularly highly criticalapplications such as the fabrication of encapsulated PWBs as describedherein, it is essential to have the solvent removed completely since theadhesive is sealed between the two surfaces it is binding together, andthere is no place to which solvent can escape without causing bubblesand voids in the finished product. Bubbles and voids adversely affectthe uniformity of the dielectric constant.

Maintaining a high degree of mixing during reaction is important forachieving full conversion of the reactants into the di-isoimide product.For example, melamine is of very limited solubility in the suitablesolvents. PMDA is also only poorly soluble. In order to achieve highconversion within a commercially viable time frame, it is necessary tomaintain good intermixing of the reactants with each other and with thesolvent. While the invention is not thereby limited, it is believed thatthe solution equilibrium for the reactants causes small amounts ofreactants to dissolve, and that the thus dissolved reactants react toform a precipitate of the di-isoimide, thereby causing additionalreactants to dissolve. This process is believed to continue until thereactants are exhausted, and conversion is quantitative as indicated bythe disappearance of the reactant peaks in the infra-red (IR)spectrograph of the solvent dispersion.

Suitable mixing can be achieved using mechanical stirring such asmagnetic stirring. A satisfactory state of mixing is one wherein thedispersion of reactants (and product) in the solvent has a uniformappearance with no regions of stagnant solids. It is preferred to stirto maintain a uniform appearance throughout the duration of thereaction.

It is found in the practice of the invention, as herein exemplifiedinfra in Examples 7 and 8, performing the first process hereof in thepresence of a rubber compound containing carboxylic acid groups insolution causes the reaction to achieve a higher rate of conversion thanthe same reaction when run without the rubber.

In a further aspect, the present invention provides a curablecomposition comprising a second solvent having mixed therewithin anepoxy and a di-isoimide composition represented by Structure I. In oneembodiment, the second solvent is the same as the first solvent.

Solvents suitable for use as the second solvent include but are notlimited to acetone, MEK, cyclohexanone, pentanone, dioxolane,tetrahydrofuran, glycol ethers, propylene glycol methyl ether acetate(PMA), N-methylpyrrolidone, N,N-dimethylacetamide, DMF, dimethylsulfoxide, N,N-diethylacetamide, N,N-diethylformamide,N,N-dimethylmethoxyacetamide. Preferred solvents are MEK, cyclohexanone,PMA, and DMF. Mixtures of solvents are also suitable.

Referring to Structure I, in one embodiment, R₁ is NH₂.

Suitable epoxies for the curable composition hereof are epoxiescomprising an average of at least two epoxide groups per polymer chain.Suitable epoxies include but are not limited to polyfunctional epoxyglycidyl ethers of polyphenol compounds, polyfunctional epoxy glycidylethers of novolak resins, alicyclic epoxy resins, aliphatic epoxyresins, heterocyclic epoxy resins, glycidyl ester epoxy resins,glycidylamine epoxy resins, and glycidylated halogenated phenol epoxyresins. Preferred epoxies include epoxy novolacs, biphenol epoxy,bisphenol-A epoxy and naphthalene epoxy. Preferred epoxies are oligomershaving 1-5 repeat units. Most preferably the epoxy is bisphenol-A ornovolac epoxy, especially bisphenol A diglycidyl ether.

Epoxies can be derivatized in any manner described in the art. Inparticular they can be halogenated, especially by bromine to achieveflame retardancy, or by fluorine.

In one embodiment of the curable composition hereof R₁ is NH₂; thesolvent is MEK, cyclohexanone, propylene glycol methyl ether acetate,DMF, or a mixture thereof; and, the epoxy is of the bisphenol-A type.

The di-isoimide represented by Structure I can serve both as a curingcatalyst and/or as a curing agent in the curable composition hereof. Theisoimide moiety reduces the flammability of the cured epoxy (vs.phenolic novolac, which does not have a comparable flame retardanteffect) and thus reduces the need for flame retadants. In oneembodiment, the curable composition further comprises a curing agent.Any curing agent known in the art can be used in the compositions andprocesses disclosed herein. Suitable curing agents include organic acidanhydrides and phenols. Monoanhydride curing agents are preferred forease of handling.

In an alternative embodiment, the curable composition hereof does notinclude a separate curing agent. It is found in the practice of thisembodiment of the invention that the nucleophilic character of the aminegroup is much reduced by the presence of the triazine ring and theisoimide linkage. It is further found that once one of the amine groupson the ring undergoes reaction, the second amine group becomes stillless reactive. Therefore in formulating the curable composition in thisembodiment, it is found that satisfactory results are achieved bytreating each mole of the di-isoimide of Structure I as representing twoequivalents from the standpoint of cross-linking the epoxy. Aformulation on that basis that contains a 20% excess in equivalents ofepoxy has been found to be satisfactory.

The curable composition hereof can include any and all of the numerousadditives commonly incorporated into epoxy formulations in the art. Thiscan include flame retardants, rubber or other tougheners, inorganicparticles, plasticizers, surfactants and rheology modifiers.

In one embodiment, the curable composition hereof comprises a lowmolecular weight liquid epoxy that serves as a dispersion medium for thedi-isoimide composition represented by Structure I. Low molecular weightepoxies, such as EPON™ Resin 828, are characterized by equivalent weightof 185-192 g/eq. However, such low molecular weight epoxies are lesspreferred than the pastier, more viscous, higher molecular weight highperformance epoxies that are well-known in the art. Higher molecularweight epoxies, such as EPON™ Resin 1001 F, are characterized byequivalent weight of 525-550 g/eq. While the reaction mixture formedfrom the higher molecular weight epoxies can be heated in order to lowerviscosity, it is undesirable to apply heat for that purpose, especiallyin the presence of a catalyst, because of the risk of causing prematurecuring. In a highly preferred embodiment a high molecular weight epoxyis dissolved in a second solvent hereof—or, less preferably dispersedtherein—into which a solution or dispersion of the di-isoimidecomposition of Structure I is then dispersed to form the curablecomposition hereof.

Suitable curing agents are phenol and aromatic anhydrides. The epoxy andthe curing agent are mixed in quantities based on their equivalentweights.

In the case of phenolic curing agents, 0.3-0.9 equivalent of phenol ispreferred for each equivalent of epoxy has been found to be suitable.With anhydride curing agents, 0.4-0.6 equivalent of anhydride ispreferred for one equivalent of epoxy.

Suitable phenol curing agents include biphenol, bisphenol A, bisphenolF, tetrabromobisphenol A, dihydroxydiphenyl sulfone, novolacs and otherphenolic oligomers obtained by the reaction of above mentioned phenolswith formaldehyde. Suitable anhydride curing agents are nadic methylanhydride, methyl tetrahydrophthalic anhydride and aromatic anhydrides.

Aromatic anhydrides curing agents include but are not limited toaromatic tetracarboxylic acid dianhydrides such as pyromelliticdianhydride, biphenyltetracarboxylic acid dianhydride,benzophenonetetracarboxylic acid dianhydride, oxydiphthalic aciddianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride,naphthalene tetracarboxylic acid dianhydride, thiophene tetracarboxylicacid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride,pyrazine tetracarboxylic acid dianhydride, and 3,4,7,8-anthraquinonetetracarboxylic acid dianhydride. Other suitable anhydride curing agentsare oligomers or polymers obtained by the copolymerization of maleicanhydride with ethylene, isobutylene, vinyl methyl ether and styrene.Maleic anhydride grafted polybutadiene can also be used as a curingagent.

Suitable tougheners are low molecular weight elastomers or thermolasticpolymers and contain functional groups for reaction with epoxy resin.Examples are polybutadienes, polyacrylics, phenoxy resin, polyphenyleneethers, polyphenylene sulfide and polyphenylene sulfone, carboxylterminated butadiene nitril elastomers (CTBN), epoxy adducts of CTBN,amine terminated butadiene nitril elastomers (ATBN), carboxylfunctionalized elastomers, polyol elastomers and amine terminated polyolelastomers. Epoxy adducts of CTBN, CTBN and carboxyl functionalizedelastomer are preferred.

In one embodiment, the di-isoimide can be pre-dispersed in the solventin which it was prepared. In an alternative embodiment, the di-isoimidemay be added as particles to the epoxy solution and dispersed thereinusing mechanical agitation.

In a further aspect, the present invention provides a second process, aprocess for preparing a cured composition from the curable compositionhereof by heating the curable composition to a temperature in the rangeof 100 to 250° C. for a period of time in the range of 30 seconds to 5hours. For adhesive applications the solvent needs to be removedcompletely before curing, as described in the Examples, infra.

The viscosity of the uncured composition can be adjusted by eitheradding solvent to decrease the viscosity, or by evaporating solvent toincrease viscosity. The uncured composition can be poured into a mold,followed by curing, to form a shaped article of any desired shape. Onesuch process known in the art is reaction injection molding. Inparticular, the composition can be used in forming films or sheets, orcoatings. The viscosity of the solution is adjusted as appropriate tothe requirements of the particular process. Films, sheets, or coatingsare prepared by any process known in the art. Suitable processes includebut are not limited to solution casting, spray-coating, spin-coating, orpainting. A preferred process is solution casting using a Meyer rod fordraw down of the casting solution deposited onto a substrate. Thesubstrate can be treated to improve the wetting and releasecharacteristics of the coating. Solution cast films are generally 10 to75 micrometers in thickness. The solution casting of asolution/dispersion hereof onto a substrate film or sheet to form alaminated article is further described in the specific embodimentshereof, infra.

In another aspect, the present invention is directed to a laminatedarticle comprising a substrate and a coating adheringly depositedthereupon wherein said substrate is a polymeric sheet or film and saidcoating comprises a curable composition comprising a second solventhaving mixed therewithin an epoxy and a di-isoimide compositionrepresented by Structure I. In one embodiment, the substrate is apolyimide film. In a further embodiment said second dielectric substrateis a fully aromatic polyimide film or sheet. In a further embodiment thepolyimide film has a thickness of 10-50 micrometers. In one embodiment,R₁ is NH₂. In one embodiment, the coating has a thickness of 10 to 75micrometers.

In one embodiment, the substrate is coated on both sides thereof. In afurther embodiment, the coatings on both sides are chemically identical.

In a further aspect, the present invention is directed to a printedwiring board comprising in order a first layer of a first dielectricsubstrate, a second layer of one or more discrete electricallyconductive pathways disposed upon said first dielectric substrate, athird layer of a bonding layer in adhesive contact with said discreteelectrically conducting pathways, and adheringly disposed upon a fourthlayer comprising a second dielectric substrate, said bonding layercomprising a curable composition comprising a second solvent havingmixed therewithin an epoxy and a di-isoimide composition represented byStructure I.

In one embodiment of the printed wiring board hereof, the first layer isa polyimide film having a thickness of 10-50 micrometers.

In one embodiment of the printed wiring board hereof, the electricallyconductive pathways are copper.

In a further embodiment of the printed wiring board hereof, the copperelectrically conductive pathways are characterized by a thickness of10-50 micrometers and lines and spacing from 10-150 micrometers.

In one embodiment of the printed wiring board hereof, in said adhesivelybonding layer said second solvent is MEK, cyclohexanone, PMA, DMF, or amixture thereof.

In one embodiment of the printed wiring board hereof, in said adhesivelybonding layer in said di-isoimide composition represented by StructureI, R₁ is NH₂.

In one embodiment of the printed wiring board hereof, the seconddielectric substrate is a polyimide film or sheet. In a furtherembodiment said second dielectric substrate is a fully aromaticpolyimide film or sheet. In a still further embodiment, said seconddielectric substrate is a film or sheet comprising a polyimide that isthe condensation product of PMDA and 4,4′-ODA. In a still furtherembodiment, said second dielectric substrate is a fully aromaticpolyimide film having a thickness of 10-50 micrometers.

The printed wiring board hereof is conveniently formed by contacting thecoating side of the laminated article hereof to the conductive pathwaysdisposed upon the first dielectric substrate. The printed wiring boardhereof has several embodiments that differ from one another in thedegree of consolidation. In one embodiment the printed wiring boardhereof is formed simply by disposing upon a horizontal surface a firstdielectric substrate having one or more discrete conductive pathwaysdisposed upon at least one surface thereof, where said conductivepathways are facing upward; followed by placing a coated side of thelaminated article hereof in contact with the conductive pathways,thereby preparing a so-called “green” or uncured printed wiring board.

In a further embodiment, the green printed wiring board is subject topressure thereby causing some consolidation. In a further embodiment thegreen printed wiring board is subject to both pressure and temperature.The temperature exposure may be sufficient to induce only a small amountof cross-linking or curing. This represents a so-called “B-stage”curing—an intermediate level of consolidation that causes the printedwiring board to have some structural integrity while retainingformability and processibility. The B-stage can be followed by completecuring. Alternatively, complete curing can be effected in a singleheating and pressurization step from the green state.

In one embodiment of the printed wiring board hereof, the firstdielectric substrate bears conductive pathways on both sides, permittingthe formation of the multi-layer construction described supra on bothsides of the first dielectric substrate.

In another embodiment of the printed wiring board hereof, the seconddielectric substrate is coated on both sides with a compositioncomprising a solution/dispersion of epoxy, a second solvent, and thedi-isoimide composition represented by Structure I.

In still a further embodiment, the first dielectric substrate bearsconductive pathways on both sides, and the second dielectric substratebears a coating on both sides, that coating comprising asolution/dispersion of epoxy, a second solvent, and the di-isoimidecomposition represented by Structure I. This embodiment permits printedwiring boards hereof to be constructed with an indefinite number ofrepetitions of the basic structure of the multilayer article.

In a further embodiment, at least a portion of the conductive pathwaysdisposed upon one side of the first dielectric substrate are inelectrically conductive contact with at least a portion of theconductive pathways disposed upon the other side of the first dielectricsubstrate through so-called “vias” that serve to connect the two sidesof the dielectric substrate.

In another aspect, the present invention provides a third process, aprocess for preparing an encapsulated printed wiring board, the processcomprising adhesively contacting the coated surface of a laminatedarticle having a surface with a coating disposed thereupon to at least aportion of the discrete conductive pathways disposed upon a dielectricsubstrate thereby forming a multilayer article; wherein said coatingcomprises a curable composition comprising a second solvent having mixedtherewithin an epoxy and a di-isoimide composition represented byStructure I; and, applying pressure to the printed wiring board soformed at a temperature in the range of 100 to 250° C. for a period oftime in the range of 30 seconds to 5 hours, thereby forming anencapsulated printed wiring board.

In one embodiment, the third process hereof further comprises extractingsaid second solvent before applying pressure to the printed wiringboard. Solvent extraction can be effected conveniently by heating in anair circulating oven set at 110° C. for a period of time ranging from2-20 minutes.

In one embodiment of the third process hereof, R₁ is NH₂.

In one embodiment of the third process hereof, the first and seconddielectric substrates are both polyimide films.

In a further embodiment of the third process hereof, the polyimide filmsare fully aromatic polyimides.

In a still further embodiment of the third process hereof, the polyimidefilms are the condensation product of PMDA and ODA.

The invention is further described in the following specific embodimentsthough not limited thereby.

EXAMPLES

Determining Reaction Completion Point

In the following examples, infrared spectroscopy (IR) was employed todetermine the end-point of the reaction. Small aliquots of the reactingmedium were withdrawn by dropper-full, dried in a vacuum oven with N₂purge at about 60° C. for about 60 minutes. Following conventionalmethodology for preparing solids for IR spectroscopic analysis, theresulting powder was then compounded with KBr followed by theapplication of pressure to the resulting compound, thereby forming atest pellet. IR absorption peaks at 1836 cm⁻¹ and 1769 cm⁻¹ weremonitored to follow the increase in the concentration of the di-isoimideproduct. Similarly, IR absorption peaks at 1856 cm⁻¹ and 1805 cm⁻¹characteristic of PMDA and 1788 cm⁻¹ characteristic of melamine weremonitored to follow the consumption of reactants. When the PMDA andmelamine peaks became undetectable, the reaction was considered to becomplete.

Peaks at 1788 cm⁻¹ and 1732 cm⁻¹ characteristic of imide were alsomonitored to follow the synthesis of any imide by-product of the presentprocess. The time to reaction completion was observed to varyconsiderably with the reaction temperature and the particular choice ofsolvent.

Reaction Medium

Both melamine and PMDA are only slightly soluble in the solventsemployed herein so it was necessary to maintain good mixing duringreaction to ensure a high degree of conversion. Without constantvigorous mixing, the solids settled and the reaction slowed down orstopped. The amount of energy that was needed for mixing was determinedby observation. When the dispersion was of uniform appearance and nostagnant solid phase was observed, mixing was deemed to be of sufficientenergy. The di-isoimide product formed into platelet particles withdimensions in the hundreds of nanometers range. These platelet particlesalso remained suspended with mixing. By the time reaction was completed,no detectable amounts of PMDA or melamine were present in the reactionmixture—all the suspended particles were di-isoimide, or, in someinstances, di-isoimide with some imide mixed in.

Printed Wiring Board

A Pyralux® AC182000R copper clad laminate sheet (Dupont Company) wasetched according to a common commercial etching process to form a seriesof parallel copper conductive strips 35 micrometers high, 100micrometers wide, and spaced 100 micrometers apart. This was used inExamples 9-12, and is referred to therein as “a PWB test sheet.”Information on methods for preparing printed wiring boards can found inChris A. Mack, Fundamental Principles of Optical Lithography The Scienceof Microfabrication, John Wiley & Sons, (London: 2007). Hardback ISBN:0470018933; Paperback ISBN: 0470727306.

Reagents

Except where otherwise noted, all reagents were obtained from SigmaAldrich Chemical Company.

Example 1

6.31 grams of melamine, 5.45 grams of PMDA and 25 grams of MEK weremixed using a magnetic stirrer in a round bottom flask. The mixture wasrefluxed under nitrogen for two days until conversion was complete. MEKwas added as needed during refluxing to keep the volume of the reactionmixture approximately constant. The thus prepared product mixture wascooled to room temperature while maintaining stirring. As confirmed byIR spectroscopy, the product mixture contained only MEK and di-isoimide.No imide was detectable. The dispersion so prepared was suitable forimmediate use in formulating a curable epoxy composition.

Example 2

6.31 grams of melamine, 5.45 grams of PMDA and 35 grams of ethyl3-ethoxypropionate were mixed in a round bottom flask. The mixture wasrefluxed under nitrogen for two days until conversion was complete. Themixture was cooled to room temperature. A small sample from the mixturewas washed with MEK. As confirmed by IR spectroscopy, the productmixture contained MEK, di-isoimide, and a small amount of imideindicated by a small IR peak at 1734 cm⁻¹. The dispersion so preparedwas suitable for immediate use in formulating a curable epoxycomposition.

Example 3

69.69 grams of melamine (0.534 moles), 60.26 grams of PMDA (0.267 moles)and 360 grams cyclohexanone are added into a reaction vessel, andstirred at room temperature for 6 days until conversion was complete. Asample from the reaction mixture was dried in vacuum oven. IR spectra ofthe final solid product showed the disappearance of the PMDA peaks at1856 & 1805 cm⁻¹ and melamine peak at 1558 cm⁻¹ and the appearance ofthe isoimide peaks at 1836 & 1769 cm⁻¹.

Example 4

6.31 grams of melamine, 5.45 grams of PMDA and 25 grams of MIBK (methylisobutyl ketone) were mixed in a round bottom flask. The mixture wasrefluxed under nitrogen for 90 minutes. The mixture was cooled to roomtemperature. A sample was dried. IR spectra of the dried sample showedthe formation of isoimide (peaks at 1836 & 1769 cm⁻¹). Reaction wascomplete to the di-isoimide and no imide was detected.

Example 5

5.81 grams of melamine, 5.00 grams of PMDA, 10 grams of DMF and 10 gramsof ethyl acetate were mixed overnight in a flask at room temperature.Reaction was complete to the di-isoimide and no imide was detected. Asmall sample was dried. IR spectra of the dried sample showed theformation of isoimide (peaks at 1836 & 1769 cm⁻¹).

Example 6

5.81 grams of melamine, 5.00 grams of PMDA, 10 grams of MIBK, and 10grams of toluene were mixed overnight in a flask at room temperature. Asmall sample was dried. IR spectra of the dried sample showed theformation of isoimide (peaks at 1836 & 1769 cm⁻¹). Reaction was completeto the di-isoimide and no imide was detected.

Example 7

3 grams of Vamac® G (from DuPont) and 12 grams of MEK were mixed in around bottom flask to form a solution. 3.30 grams of aphenol/formaldehyde resin (GP 5300 from Georgia Pacific), and 15 gramsof DMF were added to the round bottom flask, and mixed to form asolution. 3.48 grams of melamine and 3.01 grams of PMDA were added tothe solution. The solution was heated under nitrogen for 30 minutes at100° C., 30 minutes at 120° C., and 60 minutes at 140° C. The mixturewas cooled to room temperature. A small sample from the mixture waswashed thoroughly in MEK (to remove GP5300 and Vamac-G). IR spectra showthe formation of isoimide (peaks at 1836 & 1769 cm⁻¹) The anhydride andmelamine peaks disappeared while the isoimide peaks appeared, and asmall amount of imide was also present as indicated by a very small peakat 1734 cm⁻¹.

Example 8

2.90 grams of carboxyl-terminated butadiene-acrylonitrile rubber (CTBNrubber, 1300×13 from CVC Thermoset Specialties), 3.78 grams of melamine,3.27 grams of PMDA and 15 grams of dry MEK were mixed in a round bottomflask. The solution was refluxed under nitrogen for 5 hours. The mixturewas cooled to room temperature. A small sample from the mixture waswashed thoroughly in MEK (remove CTBN). IR spectra of this sample showedthe formation of isoimide (peaks at 1836 & 1769 cm⁻¹). The anhydride andmelamine peaks disappeared. A small amount of imide was present.

Comparative Example A

In a reaction vessel, 25.22 grams of melamine (0.2 moles), 21.81 gramsof PMDA (0.1 moles) and 125 ml DMF were refluxed for 5 hours. Themixture was cooled and quenched with methanol. The solid product wasfiltered and dried.

The IR spectra of the filtered solid product showed the disappearance ofthe PMDA peaks at 1856 & 1805 cm⁻¹ and of the melamine peak at 1558 cm⁻¹and the appearance of the imide peaks at 1788 & 1732 cm⁻¹.

Comparative Example B

In a reaction vessel, 50.45 grams of melamine (0.4 moles), 43.62 gramsof PMDA (0.2 moles) and 400 ml of NMP (N-methylpyrrolidinone) wererefluxed for 30 minutes. The mixture was cooled and quenched withmethanol. The solid product was filtered and dried. The IR spectra ofthe filtered solid product showed imide formation (peaks at 1788 & 1732cm⁻¹).

Example 9

3.50 grams of the di-isoimide dispersed in 9.5 grams of cyclohexanone,prepared in Example 3 supra, and 11.5 grams of a copolymer of butadieneand acrylonitrile modified to contain free carboxylic groups (Nipol1072J from Zeon Chemicals) dissolved in 63 grams of MEK, were mixed in aflask. 11.20 grams of melamine phosphate/melamine polyphosphate/melaminepyrophosphate flame retardant (Phosmel 200 Fine from Nissan ChemicalIndustries) was then added and mixed in, to form a firstsolution/dispersion. 9.10 grams of an epoxy-rubber adduct (HyPox RK84Lfrom CVC Thermoset Specialties) was dissolved in 9.10 grams of MEK toform a second solution. The second solution was added to the firstsolution/dispersion thereby forming an epoxy solution/dispersion. Theepoxy solution/dispersion so prepared was coated onto 12 micrometerthick Kapton® 50FPC polyimide film using a 7 mil gauge (177.8micrometer) doctor blade followed by removal of the solvent by placingthe thus-cast film and substrate in a vacuum oven at 60° C. for onehour, to form an approximately 25 micrometer thick coating.

The thus prepared coated Kapton® was then used as a cover-layer on thePWB test sheet. Referring to FIG. 1, the Kapton® 50FPC film, 1, coatedwith the curable composition, 2, thus prepared was contacted, 5, to thecopper conductive strips, 3, of the PWB test sheet, 4, the curablecomposition, 2, being in direct contact with the copper conductivestrips, 3. The printed wiring board thereby formed, 6, was thenconsolidated, 7, under vacuum in an OEM Laboratory Vacuum Press byholding the printed wiring board at 175° C. and 2.25 MPa for 80 minutes,thereby forming a flexible printed wiring board, 8, having fullyencapsulated copper conductive pathways.

Example 10

3.50 grams of the di-isoimide dispersed in 9.5 grams of cyclohexanone,as prepared in Example 3. and 9.80 grams of “Nipol 1072J” rubberdissolved in 55 grams of MEK were mixed in a flask. The mixture wasstirred for 30 minutes. 1.40 grams of CTBN (Carboxyl-TerminatedButadiene-Acrylonitrile Rubber, CTBN 1300×13 from CVC ThermosetSpecialties) and 11.20 grams of “Phosmel 200 Fine” flame retardant (fromNissan Chemical Industries) were added to the mixture. 9.10 grams ofHyPox RK84L were dissolved in 13.7 grams of MEK and the solution soformed was added to the mixture. The thus prepared solution/dispersionwas coated onto a 12 micrometer thick Kapton® 50ENS polyimide film usinga 7 mil gauge (177.8 micrometers) doctor blade, after which the thuscoated Kapton® film was placed into an air circulating oven at 110° C.for 10 minutes to remove the solvent. The dry adhesive film thicknesswas 27 micrometers.

The thus prepared coated Kapton® film was used to prepare a fullyencapsulated flexible printed wiring board employing the materials andprocedures described in Example 9.

Example 11

61.60 grams of “Nipol 1072J” rubber were dissolved in 350 grams of MEKin a flask to form a first solution. 9.10 grams of the di-isoimidedispersed in 25 grams of cyclohexanone prepared in Example 3 was mixedinto the first solution to form a second solution/dispersion, followedby mixing in 42.25 grams of “Phosmel 200 Fine” flame retardant (fromNissan Chemical Industries) to form a third solution/dispersion. 34.45grams of HyPox RK84L was dissolved in 34.45 grams of MEK and theresulting fourth solution was mixed into the third solution/dispersionto form a fifth solution/dispersion. 2.6 grams of bisphenol A diglycidylether epoxy resin (EPON™ 828 from Hexion Specialty Chemicals) were mixedinto the fifth solution/dispersion to form an epoxy solution/dispersion.The thus prepared epoxy solution/dispersion was coated onto a Kapton®50FPC polyimide film using a 7 mil gauge (177.8 micrometer) doctorblade. The thus coated Kapton® film was placed in an air circulatingoven at 110° C. for 10 minutes to remove the solvent. The dry coatingthickness was approximately 25 micrometers in thickness.

The thus prepared coated Kapton® film was used to prepare a fullyencapsulated flexible printed wiring board employing the materials andprocedures described in Example 9.

Example 12

55.8 grams of a cyclohexanone dispersion of melamine-PMDA di-isoimide(26.9 weight % isoimide content) prepared according to the method ofExample 3 and 51.0 grams of rubber (copolymer of butadiene andacrylonitrile modified to contain free carboxylic groups—Nipol 1072Jfrom Zeon Chemicals) were dissolved in 289 grams of MEK to form asolution. 36 grams of an epoxy-rubber adduct (HyPox RK84L from CVCThermoset Specialties) and 48.0 grams of melamine phosphate/melaminepolyphosphate/melamine pyrophosphate flame retardant (Phosmel 200 Finefrom Nissan Chemical Industries) were mixed into the solution using amechanical stirrer. When all the ingredients were dispersed into thesolution, the mixture so formed was homogenized for 2.5 minutes(Silverson model L5M homogenizer) to a dispersion having a visuallyuniform appearance. The thus homogenized mixture was then mechanicallystirred continuously until coating, described infra, was commenced.

The dispersion so prepared was coated onto Kapton® 50FPC polyimide filmusing a 7 mil gauge (177.8 micrometer) doctor blade. The solvent wasremoved by placing the thus coated Kapton® film in an air circulatingoven for 10 minutes at 110° C. The dried coating thickness wasapproximately 25 micrometers.

The thus dried coated film was laminated to a PWB test sheet. Theprinted wiring board, 6, as shown in FIG. 1 was further prepared with arelease film and a rubber pad on each side. The combination thusprepared was inserted into a quick lamination press and pressed at atemperature of 185° C. and a pressure of 9.8 MPa for 2 minutes, followedby a cure in an air-circulating oven at 160° C. for 90 minutes.

The adhesion of the coated film to the PWB test sheet was determined tobe 2.16 N/mm (Newton/millimeter) according to ISO 6133 IPC-TM-650 2.4.9using a German wheel attached to an Instron machine.

Example 13

The materials and procedures of Example 12 were employed, except thatthe quantities were different, as indicated in Table 1, and theprocedure was modified as described infra.

Ex. 12 (g) Ex. 13 (g) Melamine-PMDA isoimide (26.9 55.8 33.85 weight-%isoimide) dispersion in Cyclohexanone Nipol 1072J 51.0 41.6 MEK 289235.7 HyPox RK84L 36 34.5 Phosmel 200 Fine 48.0 42.25

The melamine-PMDA isoimide cyclohexanone dispersion, Nipol 1072J, andMEK were combined to form a first solution, to which the Phosmel 200Fine was added to form a first solution/dispersion. The HyPox RK84L wasfirst dissolved in 34.5 grams of MEK to which 2.6 grams of Epon 828(from Hexion) were added, thus forming a second solution. The secondsolution was then added to the first solution/dispersion. The remainingprocedures and method of Example 12 were then followed. The adhesion ofthe coated film on the PWB test sheet was determined to be 2.15 N/mm.

I claim:
 1. A laminated article comprising a dielectric substrate and acoating adheringly deposited thereupon wherein said dielectric substrateis a polymeric sheet or film, and said coating comprises a curablecomposition comprising a solvent having mixed therewithin an epoxy and adi-isoimide represented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.
 2. The laminated article of claim 1 wherein R₁ is NH₂. 3.The laminated article of claim 1 wherein said solvent of said curablecomposition is methyl ethyl ketone, cyclohexanone, propylene glycolmethyl ether acetate, N,N-dimethylformamide, or a mixture thereof. 4.The laminated article of claim 1 wherein, R₁ of said curable compositionis NH₂; the solvent of said curable composition is methyl ethyl ketone,cyclohexanone, propylene glycol methyl ether acetate,N,N-dimethylformamide, or a mixture thereof; and, the epoxy of saidcurable composition is a bisphenol A diglycidyl ether.
 5. The laminatedarticle of claim 1 wherein said curable composition further comprises anelastomer, a thermoplastic polymer, or a combination thereof.
 6. Thelaminated article of claim 1 wherein said dielectric substrate is afully aromatic polyimide film or sheet.
 7. The laminated article ofclaim 6 wherein said aromatic polyimide film or sheet is characterizedby a thickness in the range of 10 to 50 micrometers.
 8. The laminatedarticle of claim 6 wherein said fully aromatic polyimide film or sheetcomprises a polyimide that is the condensation product polymelliticdianhydride and 4,4′-oxydianiline.
 9. The laminated article of claim 1wherein said coating is characterized by a thickness in the range of 10to 75 micrometers.
 10. The laminated article of claim 1 wherein saidsubstrate further comprises a first surface and a second surface,wherein said first surface comprises a first coating adheringly disposedthereon; and, wherein said second surface comprises a second coatingadheringly disposed thereon.
 11. The laminated article of claim 10wherein each of said first and second coatings comprises the curablecomposition comprising the solvent having mixed therewithin the epoxyand the di-isoimide represented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.
 12. A laminated article comprising a substrate and acoating adheringly deposited thereupon wherein said substrate is apolymeric sheet or film and said coating comprises a curable compositionconsisting essentially of a solvent having mixed therewithin an epoxyand a di-isoimide represented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.
 13. The laminated article of claim 12 wherein R₁ is NH₂;the solvent is methyl ethyl ketone, cyclohexanone, propylene glycolmethyl ether acetate, N,N-dimethylformamide, or a mixture thereof; and,the epoxy is a bisphenol A diglycidyl ether.
 14. A laminated articlecomprising a substrate and a coating adheringly deposited thereuponwherein said substrate is a polymeric sheet or film and said coatingcomprises a curable composition comprising a solvent having mixedtherewithin an epoxy; an elastomer, a thermoplastic polymer orcombination thereof; and a di-isoimide represented by Structure I

wherein R₁ is H, halogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,amido, sulfonamido, cyclic amino, acyl, morpholino, piperidino, or NR′R″where R′ and R″ are independently H, alkyl or aromatic, substituted orunsubstituted.
 15. The laminated article of claim 14 wherein R₁ is NH₂;the solvent is methyl ethyl ketone, cyclohexanone, propylene glycolmethyl ether acetate, N,N-dimethylformamide, or a mixture thereof; and,the epoxy is a bisphenol A diglycidyl ether.